Renewable bio-based (meth)acrylated monomers as vinyl ester cross-linkers
Inventors
Palmese, Giuseppe R. • La Scala, John Joseph • Sadler, Joshua Matthew • Lam, Anh-Phuong Thy
Assignees
Drexel University • United States Department of the Army
Publication Number
US-10053529-B2
Publication Date
2018-08-21
Expiration Date
2032-08-10
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Abstract
Anhydrosugar-based monomers prepared from isosorbide, isomannide, and isoidide and resin systems containing these anhydrosugar-based monomers that are partially to fully bio-based, which may produce materials having properties that meet or exceed the properties of similar petroleum derived vinyl ester resins.
Core Innovation
The invention relates to novel anhydrosugar-based monomers derived from isosorbide, isomannide, or isoidide, which are plant cellulose or carbohydrate-based renewable sources. These monomers serve as low viscosity cross-linkers for thermoset vinyl ester resins, enabling partially to fully bio-based resin systems. The monomers have relatively low molecular weights due to the confined bicyclic core structure, which results in reduced viscosities for vinyl ester resins, thereby minimizing or even eliminating the need for hazardous reactive diluents like styrene.
The problem addressed is the reliance on petroleum-based vinyl ester resins and hazardous reactive diluents that are environmentally harmful and have regulated use due to their status as Hazardous Air Pollutants (HAPs) or Volatile Organic Compounds (VOCs). Petroleum-based resins typically have high viscosities requiring reactive diluents for processing, while bio-based resins have not successfully produced low viscosity formulations without compromising toughness or requiring high diluent contents. Therefore, there is a need for bio-based vinyl ester resins that offer excellent processability, suitable toughness, and reduced reactive diluent dependency.
The invention further includes synthetic routes to produce these anhydrosugar-based monomers, including acrylation, methacrylation, maleination, and functionalization of epoxide intermediates, resulting in monomers with multiple polymerizable sites. These monomers can be used individually or in blends with petroleum-based or bio-based reactive diluents and vinyl ester resins to adjust viscosity, toughness, and glass transition temperature (Tg). The monomers can polymerize to form linear, branched, hyperbranched, or cross-linked polymers exhibiting similar or improved mechanical properties compared to petroleum-based counterparts.
Claims Coverage
The patent includes two primary independent claims focusing on methods of making polymers using novel bio-based monomers and methods of making polymers from blends with vinyl ester or unsaturated polyester monomers. The main inventive features involve the composition formulations and curing methods for these polymers.
Method of curing composition with specific polymerizable monomers
A method of making polymers by curing a composition comprising at least one polymerizable monomer selected from specific anhydrosugar-based structures derived from isosorbide, isomannide, or isoidide capable of free radical polymerization.
Polymerization with vinyl ester resin or unsaturated polyester monomers blended with anhydrosugar-based monomers
A method of making polymers by curing compositions containing 1-99% by weight of anhydrosugar-based monomers, 1-70% vinyl ester or unsaturated polyester monomers, and 0-60% reactive diluents, wherein the anhydrosugar-based monomers have specified chemical formulas and the compositions can be varied to tailor polymer properties.
The claims collectively cover the use of anhydrosugar-based polymerizable monomers alone or in blends with vinyl ester or polyester monomers and reactive diluents, cured mostly by free radical methods, to produce polymers with mechanical and thermal properties comparable or superior to petroleum-based analogs.
Stated Advantages
Reduced viscosity of vinyl ester resins allowing minimal use of hazardous reactive diluents, improving processability and environmental profile.
Production of polymers having stiffness, toughness, and glass transition temperatures similar or superior to petroleum-derived vinyl ester resins.
Use of renewable bio-based monomers reduces dependency on petroleum and enhances sustainability of resin systems.
Capability to modulate viscosity and enhance glass transition temperature (Tg) in vinyl ester resin formulations.
Documented Applications
Use in producing thermosetting vinyl ester resins for adhesives and resin matrices for fiber reinforced composites.
Application in liquid molding, composite layups, and vacuum assisted resin transfer molding (VARTM) due to tunable low viscosities.
Formation of polymer matrix composites for military, automotive, recreational, and marine applications including vehicle body panels, armor, composite hoods, and boat hull structures.
Use as gel coating materials for protective coatings on composites and other surfaces.
Polymerization into linear, branched, hyperbranched, and cross-linked polymers useful in biosensors, rheology modifiers, biomaterials, and polymerizable surfactants for media encapsulation.
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